Cellulose fibers and process of treating them



Patented Nov. 2, 1943 CELLULOSE FIBER-S AND PROCESS OF TREATING THEMErik Sehirm, Dessau in Anhalt, Germany, as-

signor, by mesne assignments, to General Aniline 8.: Film Corporation,New York, N. Y., a corporation of Delaware No Drawing. Application July24, 1937. Serial No. 155,571. In Germany September 28, 1932 4 Claims.

This application is a continuation-in-part of V U. S. patent applicationSerial No. 690,034, (now U. S. P. No. 2,120,267) filed September 18,1933, in the name of Erik Schirm.

The invention relates to the improvement of cellulose materials; moreparticularly, it relates to enhancing the colorability of natural orregenerated cellulose. It is an object of the invention to improvecellulose materials by exposing them to the simultaneous action ofaldehydes and ketones and of derivatives of aldehydes and ketones andheterocyclic bases or their salts-with strong acids, for instance,pyridines and quinolines, or isoquinolines. By strong acids the mineralacids are meant in general, yet one may likewise employ organic sulfonicacids or ester acids derivable from poly-basic mineral acids. If in thiscase one chooses sulfonic or ester acids, the hydrocarbon residue ofwhich corresponds to soap-forming carboxylic acids, such ascetylsulfonic acid, octadecyl-sulfuric acid, sulforicinolor sulfo-oleicacid, one obtains simultaneously with the forming of the amine yarn alsoa softening efiect.

By the treatment according to the present invenin'on hydrophobicproperties are in many cases imparted to the fibers, particularly incase compounds containing a high molecular aliphatic radical are used.

In employing such aldehydeor ketone derivatives which may be consideredas esters of strong acids, such as chloromethyl acetate,ethylidenebromide, benzal chloride or alpha-halogen ether of the generalformula (X=halogen, R and R represent aryl radicals or aliphatichydrocarbon radicals such as; alkyl, cycloalkyl, aralkyl, R alsohydrogen), such as butylchloromethyl ether, the mere presence of thefree pyridine base will suiiice, the latter being obviously transformedby itself in the reaction mixture into the corresponding salt, 1. e.into the chloror prom-hydrate, respectively.

In some cases reaction occurs easily between the aldehydeor ketonederivatives and the heterocyclic bases. When compounds of the formulasuch as mentioned above, are used, there may be formed additioncompounds of the following formula For th present process there may, ofcourse, be used these addition products instead of theindividualcomponents.

The conversion is advantageously done in presence of indifierentdiluents. For this purpose the pyridine bases which are destined for theconversion, may be employed, in a free form, as well as the.hydrocarbons, chlorinated hydrocarbons, nitrobenzene and similarmaterials which are much in use as diluents. The presence of certainamounts of the free base besides its salt has proved advantageous withregard to the preservation of the fiber.

The temperatures at which the reactions are conducted vary according tothe reaction capacity of the aldehyde or ketone or derivative employed.Formaldehyd and its derivatives react the most easily, generally attemperatures of less-than 0., whereas the other aldehydes and theketones as well as their derivatives require somewhat highertemperatures.

On employing monomerous, low aliphatic aldehydes and ketones andderivatives the process is preferably conducted in closed vessels andunder pressure. The same procedure should be followed when working witheasily volatile pyridine bases, e.'g. pyridine itself and/or diluentsboiling at low temperatures such as chloroform or trichloroethylene, ifthe reaction does not occur at all or rapidly enough at theirboilingpoints.

Some illustrative examples for the treatment of cellulose are givenbelow, followed by a description of the improvement in the dyeingproperties of the treated cellulose. They only serve to illustrate thinvention and are not intended to limit it thereto; the parts are byweight:

(1) 1 parts of ethylidenediacetate is mixed with 30 parts of a mixtureof pyridine bases such as are used for making denaturated alcohol,whereupon 1 part of pyridine hydrochloride is added. Two parts of cottonare then added and the whole is heated for 4 hours to C., whereupon thecotton is separated from the reaction mixture and washed and dried.

The ethylidenediacetate may be replaced by acetal.

(2) 1 part of benzalchloride, 1 part of cotton and 20 parts of pyridineare boiled for 7 hours at the reflux-cooler. The separation and aftertheehloromethylor alpha-chloroethyl ethers, respectively, of other alcoholssuch as methyl-,

' may likewise employ with the same good result ethyl-, propyl-, amyl-,cyclohexylor benzylalcohol (4) 2 parts of dry pyridine are introducedinto a solution of 2 parts of hexadecylchloromethyl ether in 250 partsof carbon tetrachloride and cotton material is treated'for 20 minuteswith this solution. Thereupon, the material is centrifuged anddried at100 C. to 110 C.

(5) Artificial silk crepe is impregnated for minutes at ordinarytemperature with an aqueous solution of 1 per cent. strength of theaddition product of stearylchloromethyl ether and pyridine. The goodsare then squeezed and heated for 1 hour at C. to C.

As to the colorability the cellulose fiber preliminarily treatedaccording to the present invention is like the so-called amine-yam," i.e. it is dyed directly by all dyestuffs and dyestuff intermediates of anacid character, therefore by the direct cotton dyestuffs, the so-calledacid wool dyestuffs, further by mordant dyestuffs, such as aiizarine,logwoodor yellowwood extract and others, by sulfuric acid ester salts ofvat-dyestuifs (indigosoles"), by the 2:3-hydroxynaplithoic acid-arylidesetc.

The present invention, therefore, facilitates the manufacture of equaldyeingson mixturefabrics made of cellulose fiber and animal fiber, sinceit places at ones disposal a richer selection of dyestuffs which possessabout the same drawing power for the animal fiber as well as for thecellulose fiber preliminarily treated according to the invention.

Substantive ,dyestufls draw on the new yarn by far more energeticallythan onordinary cellulose flber and these dyeings are in many casesconsiderably faster to washing than on ordinary cellulose fiber; thismay be explained by the fact, that the dyestuif owing to its specialconstitution is not only adsorbed by the cellulose (as it is also thecase with ordinary substantive dyeings) but simultaneously alsochemically bound to the substrate by its sulfo-groups as a quaternaryammonia salt.

If a preliminarily treated and wetted material is brought into a coldbath which contains in the usual bath length (1:10 to 1:20) or in alarger one the usual percentages of its weight of any substantivedyestuif (e. g. Congo-red, Diamine-brown M, Diamine-blue BB; Schultz-Julius, Farbstofitabellen 1914, Nr. 307, 344, 337, and others), thedyestufi draws in a short time completely on the fiber, even in theabsence of the otherwise usual admixtures, such as common salt, sodiumsulfate, sodium carbonate etc. These dyeings are much faster tovwashingthan those on ordinary cellulose. Also non-substantive acid assasos thecold, whereas other ones such as Raphthyl amine black D (Schultz-Julius,loc. cit. Nr. 86). drawonbetterwhenwamataboutwc. One can also observe,that dyestuffs capable of drewing on completely or nearly completelywhen 'cold,arepartiallybleedingoutduringtheheating ofthebath,wheressoncoolingdownthehath they again draw on entirely. with regrd to the uniform dyeing it is, however, to perform the dyeings as'usualin a heated bath.

The usual methods to enhance the fastness to washingofdyeingsonthecellulosefiberconsistingindiazotizingthedyestuffonthefiberand in developing with aso-components,as well as the after-treatment of suitable dyestuffs on the fiber withdiazonium compounds, may likewise beadoptedforthecellulosefiberpreliminarily treated according to the invention,but the circle of the dyestuffs considered for the purpose is thenconsiderably enlarged. Thus, as an example, it is possible to diasotiseon the fiber a dyeing of Naphthylamine-black D (see above) used hithertoonly as wool dyestuff, and to develop with an alkaline solution ofbeta-naphthol to a neutral dark black. In an analogous manner thedyestuif Naphthylamine-brown S (Schultz- Julius, loc. cit. Nr. canbedyed on and developed with diazotized para-nitraniline to a washing-fastbrown.

Also the chrome development-dyestuffs for wool, such as Eriochrome-red B(schultv-Julius, loc. cit. Nr. 29) can be dyed upon the new yarn anddeveloped with chromates in the well-known dyestuifssuch as Orange II,Fast-red A, Alizarine I manner during or after the dyeing and preferablyin a slightly acid solution.

Particularly remarkable is the further fact, that not only dyestuffs andtheir intermediates but also 'other compounds with acid propertiespounds, are bound by the fiber preliminarily treated according to thepresent invention. Moreover, it is remarkable that those of theaforementioned classes of materials which possess the properties ofsoaps or soap-formers, produce quite excellent softening and smoothingeffects. Arparticular advantage of this smoothing and softening comparedwith that on ordinary cellulose, consists, on the one hand, in that itis perfectly fast to the washing, since the soaps or soap-like productsemployed for the washing operation exert a smoothing and softeningaction upon the new yarn, on the other hand, one can simultaneously dyeand smooth or soften the yarn by adding the dyestuff and smoothing orsoftening agent to the treatment bath in the desired proportions, and'then proceeding in the usual way.

' I claim:

1. The process of enhancing the colorability of natural and regeneratedcellulose which comprises treating the fibers at an elevated temperaturewith compounds of the group consisting of pyridines and quinolines inthe presence of an indiiferent diluent, as which the aforesaid bases mayserve themselves, and simultaneously with a compound of the formula:

wherein R" represents a member of the group consisting of aliphatichydrocarbon radicals containing up to six carbon atoms and benzyl. andHal represents halogen.

2. The process of enhancing the colorability of natural and regeneratedcellulose which comprises treating the fibers at an elevated temperaturewith compounds of the group consisting of pyridines and quinolines inthe presence of an indifierent diluent, as which the aforesaid bases mayserve themselves, and simultaneously with compounds of the formula:

consisting of hydrocarbon radicals containing up to six carbon atoms andbenzyl, Hal represents halogen and Y stands for a member of the groupconsisting of hydrogen a (1 methyl.

3. Cellulose textile m'a rials having improved colorability and waterrepellent properties and being the product of the process as defined inclaim 1.

4. Cellulose textile materials having improved colorability and waterrepellent properties and being a product of the process as defined inclaim 1. V

ERIK SCHIRM.

Certificate of Correction Patent No. 2,333,203. November 2, 1943. ERIKSCHIRM It is hereby certified that errors appear in the printedspecification of the above numbered patent requiring correction asfollows: Page 1, first column, line 40, after radicals insert a comma;and second column, line 43, for 1 parts read 1 part; age

3, second columni line 1, before hydrocarbon insert aliphatic; line 12,for the aim 7 reference numera 1 read 2; and that the said LettersPatent should be read with these corrections therein that the same mayconform to the record of the case in the Patent Ofiice.

Signed and sealed this 11th day of June, A. D. 1946.

[sent] LESLIE FRAZER,

First Assistant Commissioner of Patents.

